CN2100627U - Palladium ph electrode - Google Patents
Palladium ph electrode Download PDFInfo
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- CN2100627U CN2100627U CN 91202825 CN91202825U CN2100627U CN 2100627 U CN2100627 U CN 2100627U CN 91202825 CN91202825 CN 91202825 CN 91202825 U CN91202825 U CN 91202825U CN 2100627 U CN2100627 U CN 2100627U
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- palladium
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Abstract
The utility model discloses a palladium pH measuring electrode belonging to the measuring technique for pH value of solution. The electrode can be used for replacing a glass electrode to be used for measuring the pH value of solution in various technological departments. The electrode is provided with a palladium film or a palladium silk at the lower end of a glass tube by a sealing mode. The palladium film or the palladium silk is led out from the tube with an insulating stainless steel wire. Sodium sulfate electrolyte and a platinum electrode are arranged in the tube. When the platinum electrode and the palladium electrode are electrolyzed, hydrogen gas is generated at the side of the palladium film in the tube, hydrogen is diffused to the outer side, the hydrogen and hydrogen ions in the solution whose pH value is measured form an electric potential, the electric potential is measured, and the pH value of the solution which is measured can be directly indicated. The electrode has the advantages of stable and firm performance, low internal resistance, wide applicability, accurate measured value, convenient use, etc.
Description
The present invention is a palladium pH electrode, belongs to pH value of solution value measuring technique.This electrode can replace glass electrode and it plants metal electrode in departments such as chemistry, biology, medical science, environmental protection, food hygiene, chemical engineering, is used for the measurement of pH value of solution value and the sensing original paper of pH value.
Before the present invention occurred, appearance that can this spy (Nerngt) equation connected the primary element phenomenon in thermodynamics and the galvanochemistry, thereby provided theoretical foundation for the measurement of pH value of solution value.The pH potential electrode with practical value that people adopted has: H(Pt) electrode, quinone---quinhydrone electrode, antimony electrode (limitation is bigger), glass electrode etc.Glass electrode can be applicable to the number of chemical environment, meets Nernst equation in pH2～12 scopes, up to the present, it be popular among the people reach 40 surplus year.But still there are some shortcomings in glass electrode, and these shortcomings are: 1. when measuring than strong acid-base, the pH value exists acid, alkaline error; 2. glass electrode internal resistance higher (the over thousands of megohm of tens of megohms to); 3. frangible; 4. because the thermodynamic phase of glass structure, glass crystallization and make electrode failure progressively in electrode is made back one to two year.
The purpose of this utility model provides a kind of pH electrode with following multiple advantage--palladium pH electrode.Its advantage is: 1. have thermodynamic stability, can prolonged and repeatedly use; 2. sound construction; 3. internal resistance is low; 4. measured value meets Nernst equation and accurately constant; 5. need not soak before using; 6. be applicable to the number of chemical environment; 7. can use existing pH meter to measure.So this electrode is the once change of pH potential electrode evolution.
Palladium pH electrode is consistent with the principle of hydrogen (Pt) electrode measurement pH value of solution value, promptly to measure Pd, H
2H
+Phase boundary potential as the foundation of judging the pH value of solution value.But the required hydrogen of this electrode is to adopt electrolytic method to produce in palladium film one side, utilize hydrogen to dissolve in palladium and can be diffused into the effect of opposite side, thereby with opposite side solution to be measured in aH
+Form stable phase boundary potential.The method for making that this method has hydrogen is easy, high-purity, stable; And be dissolved in hydrogen in the palladium when the opposite side of palladium forms current potential with hydrogen ion at the interface, show higher pressure, make current potential to positive dirction moved about 600 surplus millivolt, thereby avoided different kinds of ions such as Fe
3+Deng influence with higher oxidation one reduction potential; In solution to be measured, do not separate out because of hydrogen again, so just eliminated the shortcoming of hydrogen (Pt) electrode.
The molten dark pH value principle of palladium pH electrode measurement as shown in Figure 1, an amount of metabisulfite solution is housed in palladium electrode a, and platinum electrode 2 in electrode glass-tube 1 and 3 of pipe end palladium films pass to constant dc current makes water electrolysis, and oxygen is separated out at platinode, hydrogen diffuses to the H in the outside and the solution to be measured in the inboard generation of palladium film pipe
+Set up H
2/ a
H+Current potential, the mercurous chloride electrode b pairing in this phase boundary potential and the solution to be measured forms primary element, and the primary element electromotive force is sent into existing glass one mercurous chloride electrode pH meter after potentiometer 8 is regulated, locate and measure the pH value of solution to be measured by identical localization method.
One. power supply and measurement loop
The electrolytic hydrogen production of palladium electrode partly needs constant-current supply, and for the pH current potential with palladium electrode is adjusted to the purpose that can be used with the pH meter of existing glass electrode, need use constant pressure source.The inventor has designed simple single-point connection two-circuit as shown in Figure 2 for this reason.
This circuit is through several months energising work examination, prove reliable and stable, all earth points in the circuit (being negative pole) should join being aligned but really ground connection draw the glass electrode jack that connects glass electrode pH meter by the wiping end 10 of 4.7K potentiometer 9 at last.
Two. description of drawings
Fig. 1 palladium electrode principle of work
A. palladium electrode; B. mercurous chloride electrode; 1. palladium electrode glass-tube; 2. platinum electrode; 3. palladium film; 4. Stainless Steel silk and thin glass tube sleeve pipe; 5. metabisulfite solution; 6. pH value solution to be measured; 7. electrolytic hydrogen production power supply in the palladium electrode; 8. current potential is regulated; 9. connect the pH measuring instrument.
Fig. 2 power supply and working line
1. two 8 volts of transformers; 2.1A diode; 3.100 electrolytic dissolution device μ F(50 volt); 4.7808 integrated package of pressure-stabilizing; 5.3DX201 transistor; 6. palladium electrode; 7.20K adjustable potentiometer; 10. connect pH meter glass electrode jack.The parallel connection of (notes) negative pole is earth-free.
Fig. 3 palladium electrode structural map one
1. electrode glass-tube; 2. platinum electrode; 3. palladium film; 4. stainless steel wire and thin glass bushing; 5. palladium film external insulation enamelled coating and tygon sleeve pipe; 6. metabisulfite solution; 7. epoxy resin;
8. end cap; 9. electrode cable; 10. plug; 11. filling opening.
Fig. 4 palladium electrode structural map two
1. electrode glass-tube; 2. filling opening; 3. platinum electrode; 4.U shape end plating palladium silk (or palladium silk); 5. Stainless Steel silk and thin glass tube sleeve pipe; 6. at the bottom of the glass film pipe; 7. metabisulfite solution; 8. epoxy resin; 9. end cap; 10. electrode cable; 11. plug; 12. tygon protection pipe box.
Three. the structure of palladium electrode
1. the palladium electrode structure one
As shown in Figure 3, electrode tube is a glass-tube, and its lower end is slightly thin, and about 5 millimeters of external diameter is the cartridge position herein.Cartridge is the cover that a palladium film (sheet) forms, and makes electrode glass-tube lower end become a cecum.The cover inwall relies on copper coating and electrode glass-tube close-coupled.Palladium cover outside is from the enamelled coating that insulate admittedly, and the enamelled coating outside is a tygon protection short tube.Can not there be coverture at palladium film (sheet) pipe outer side center position, the end.In the electrode tube inboard, palladium film (sheet) is gone up with a Stainless Steel silk and is closely welded, and steel wire is with a thin glass tube, more than is the palladium cartridge.
Except that above-mentioned Stainless Steel silk, a platinum electrode is arranged still in the pipe, the two is connected with two strands of insulated conductor respectively in electrode tube upper end, and has end cap to fix another termination two-wire plug of lead with epoxy resin in electrode mouth of pipe upper end.
There is a filling opening (being exhausr port simultaneously) the electrode tube side, adds electrolyte solution (for example metabisulfite solution) by filling opening, and this filling opening clogs with rubber stopper when electrode does not use, and removes during use.
2. the palladium electrode structure two
As shown in Figure 4, electrode glass-tube lower end is slightly thin, about 5 millimeters of external diameter, and make the pipe lower end become a cecum at the bottom of a glass-film is arranged, be the cartridge position herein.Cartridge is that a lower end curves U-shaped and is coated with the Stainless Steel silk (or band) of palladium layer in the U-shaped place, this U-shaped plating palladium silk (also available pure palladium silk or band) is by passing in the pipe at the bottom of the glass-film outside the fairlead, get back in the pipe at the bottom of passing glass-film more again, stay one section outside the glass-film bottom, this palladium silk is anchored on the glass-film bottom and forms cartridge.The Stainless Steel silk partly is with thin glass tube in pipe, cartridge is with tygon protection short tube outward.
Except that above-mentioned Stainless Steel silk, platinum electrode is arranged still in the pipe, two strands with insulated conductor link in the electrode tube upper end for the two, and have end cap to fix another termination two-wire plug of lead with epoxy resin in electrode mouth of pipe upper end.
There is filling opening (being exhausr port simultaneously) the electrode tube side, adds electrolyte solution (for example metabisulfite solution) by filling opening, and this filling opening clogs with rubber stopper when electrode does not use, and removes during use.
Four. the making of palladium electrode
1. the making of palladium electrode structure one
As shown in Figure 3, the electrode glass-tube is blow molded into " 95 " glass-tube, and the lower end is slightly thin, about 5 millimeters, side pipe is arranged.
Palladium cartridge: earlier the glass-tube lower end is polished; the sand hair; chamfered edge; and in the distance lower end 4 millimeters locate to carve an annular groove; plate a bronze medal layer in cutting to lower end with chemical method; with electrochemical plating the copper layer is thickeied again; with garden shape palladium sheet; Stainless Steel silk lower end in the pipe; copper plate lower end three is welded into the cartridge pipe box; then with the whole copper facing of cartridge; integral body is coated with one deck temporary protection insullac again; at mouth of pipe lower end enamelled coating central part; lacquer is removed a little garden sheet, the copper layer at sheet place, little garden is removed that (electrochemical erosion method is to do anodally with mouth of pipe place, carries out electrolysis with the ammonia metabisulfite solution with electrochemical erosion method; making the copper layer become ammoniacal copper complex ion dissolves); coat with lacquer protective seam with the caustic lye of soda flush away temporarily,, make to become a palladium cover with the palladium sheet again with the whole plating of cartridge palladium; the outside is coated with insullac but bottom centre's palladium film is exposed admittedly certainly, and it is outer protects short tube for tygon.
Electrode tube is installed: the platinum electrode of packing in the above-mentioned glass-tube that performs the palladium cartridge, cover one thin glass tube on the Stainless Steel silk, this two electrode upper end link to each other with two strands of insulated conductor respectively, and the lead other end links to each other with two-wire plug, end cap is installed, with epoxy resin with electrode tube upper end sealing.
In the electrode tube on the palladium sheet because of welding operation often with metals such as scolding tin, can in electrode, inject the ammonia metabisulfite solution through filling opening, be that anodal, platinum is that negative pole carries out electrolytic corrosion with the palladium, this method can be removed other metal on the palladium totally.
To clean in the electrode tube with deionized water, inject nearly saturated metabisulfite solution, with rubber stopper that the filling opening plug is good, this plug takes off in use.So far whole manufacturing process of palladium electrode are finished.
2. the making of palladium electrode structure two
As shown in Figure 4, the electrode glass-tube has side pipe with the blowing of " 95 " glass-tube, and the lower end is slightly thin, about 5 millimeters of external diameter.
Palladium cartridge: Stainless Steel silk (or band) lower end is curved U-shaped, at U-shaped position copper electroplating layer, plate palladium layer (also available pure palladium silk " band ") again, plating palladium layer thickness requires 30～80 microns, respectively fire a bead with " 95 " glass fiber at middle part, plating palladium silk U-shaped both sides, with suitable height in this electrode glass-tube of packing into, at bead position burning glass back cover film, make plating palladium silk have half to stay in the electrode tube, half of U-shaped bottom stayed outside the electrode tube.Thin glass tube on the Stainless Steel silk braid in the pipe, cartridge are installed tygon protection short tube.
Electrode tube is installed: platinum electrode is housed in pipe, and its upper end and Stainless Steel silk upper end are connected and draw from the upper end with two strands of electrode cable respectively, connect two-wire plug, and the installation end cap is used the epoxy resin sealing.
Inject electrolyte solution (for example metabisulfite solution) in from filling opening toward pipe, filling opening is clogged, remove during use, so far all complete with rubber stopper.
Five. the palladium electrode current potential is with pH value of solution value change curve
The palladium electrode current potential according to experimental fact, proves to meet Nernst equation, promptly
φ＝φ
0－2.303× (RT)/(F) ×pH
The implication of each symbol is all identical with used symbol in the general physical chemistry book in the formula.The variation of atmospheric pressure, electrolysis is the variation of strength of current partly, all influences φ
0Value.The particularly variation of palladium membrance current density is to φ
0The influence of value is particularly evident.The variation of atmospheric pressure and current density all is the influence to hydrogen pressure in fact.When adopting constant-current supply at room temperature to carry out electrolysis, current potential φ value is very stable.Different electrodes, φ
0Value is different.From performance, not this and glass electrode not similar to scalar potential.When adopting present various pH meter to measure, the steady arm on also available this pH meter positions palladium electrode.
The performance of palladium pH electrode is described for the sake of simplicity and directly, and it is as follows now to get 221 type glass electrodes and palladium pH electrode comparative determination that Jiangsu Electrical Analysis Instrument Factory dispatched from the factory on March 23rd, 1989:
PH meter model: SP-1 type SOLUTION PROPERTIES: buffer solution
Measure temperature: 30 ℃ of location pH values: 6.85
| Type of electrodes | The pH value | |||||
| 221 type glass electrodes | 1.46 | 3.20 | 4.00 | 6.85 | 8.20 | 9.85 |
| No. 1, palladium pH electrode | 1.15 | 3.18 | 4.00 | 6.85 | 8.21 | 9.86 |
| No. 2 | 1.16 | 3.18 | 4.00 | 6.85 | 8.20 | 9.86 |
| No. 3 | 1.15 | 3.18 | 4.00 | 6.85 | 8.21 | 9.86 |
PH meter model: SP-1 type SOLUTION PROPERTIES: buffer solution
Measure temperature: 20 ℃ of location pH values: 6.86
| Type of electrodes | The pH value | |||||
| 221 type glass electrodes | 1.47 | 3.21 | 4.01 | 6.86 | 8.21 | 9.86 |
| No. 1, palladium pH electrode | 1.16 | 3.19 | 4.01 | 6.86 | 8.22 | 9.87 |
| No. 2 | 1.17 | 3.19 | 4.01 | 6.86 | 8.21 | 9.87 |
| No. 3 | 1.16 | 3.19 | 4.01 | 6.86 | 8.22 | 9.87 |
Palladium pH electrode except that nitric acid, chloroazotic acid or contain the acid solution of strong oxidizer such as the potassium permanganate acid solution in can not use, very convenient accurate in order to measure pH value of solution value in the ordinary course of things.
Claims (4)
1, a kind of palladium pH electrode, its architectural feature is: cartridge place, electrode tube lower end hard-pressed bale palladium film (sheet) or fastening plating palladium silk (band), silk (band) also can be made of pure palladium, purpose is when electrolysis, palladium film in cartridge (or silk) locates to produce hydrogen, and hydrogen is dissolved in palladium, the H in the cartridge outside and solution
+Form current potential, in order to measure the pH value of solution.
2, the palladium pH electrode according to claim 1 is characterized in that: platinum electrode and electrolyte solution (as metabisulfite solution) also are housed in the pipe, are that anodal palladium is that negative pole carries out electrolysis with platinum, at the inboard hydrogen that produces of palladium utmost point pipe.
3, according to claim 1,2 palladium pH electrode; its architectural feature is: outside the glass-tube at electrode tip place; closely be with the cover that palladium film (sheet) is made; the side of palladium Membrane cover in pipe connects with insulated conductor and drawn by the upper end; the palladium cover diaphragm outside scribbles insullac (but the centre is exposed at the bottom of the palladium diaphragm pipe), and there is the insulation protection short tube outside.
4, according to claim 1,2 palladium pH electrode; its architectural feature is: cartridge position, electrode tube lower end glass membrane closure; to plate palladium silk (band); also available pure palladium silk (band); passing the glass film is fixed on the glass film back cover; the palladium silk is a termination insulated conductor in pipe, is the exposed end of palladium silk outside pipe, and cartridge has the protection pipe box.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91202825 CN2100627U (en) | 1991-02-22 | 1991-02-22 | Palladium ph electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91202825 CN2100627U (en) | 1991-02-22 | 1991-02-22 | Palladium ph electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN2100627U true CN2100627U (en) | 1992-04-01 |
Family
ID=4913282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91202825 Withdrawn CN2100627U (en) | 1991-02-22 | 1991-02-22 | Palladium ph electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN2100627U (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422728C (en) * | 2006-03-28 | 2008-10-01 | 浙江大学 | Metal antimony oxide electrode and method for tracking and detecting medium pH change |
| CN101813659A (en) * | 2009-02-20 | 2010-08-25 | 厦门大学 | Preparation method of palladium black-hydrogen pH microelectrode |
| CN103018295A (en) * | 2012-11-23 | 2013-04-03 | 深圳大学 | Constant-potential solid pH detector |
-
1991
- 1991-02-22 CN CN 91202825 patent/CN2100627U/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422728C (en) * | 2006-03-28 | 2008-10-01 | 浙江大学 | Metal antimony oxide electrode and method for tracking and detecting medium pH change |
| CN101813659A (en) * | 2009-02-20 | 2010-08-25 | 厦门大学 | Preparation method of palladium black-hydrogen pH microelectrode |
| CN101813659B (en) * | 2009-02-20 | 2013-02-13 | 厦门大学 | Preparation method of palladium black-hydrogen pH microelectrode |
| CN103018295A (en) * | 2012-11-23 | 2013-04-03 | 深圳大学 | Constant-potential solid pH detector |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |